1186 H.
GREENE
CHARLES
curves as they stand, with few comments, pending
further work on the preparation and study of the
much needed nitroso derivatives of the methyl
naphthyl ethers. It does seem in each case, how-
ever, that the curve .of the tautomeric mixture re-
sembles the curves of the quinonoid types more
closely than those of the benzenoid types.
Elnperimental
No new or unpublished methods were used in
the preparation of the compounds studied. Each
was purified carefully. The solvents were also
purified so that they were optically clear through-
out the range of the spectrum for which they were
used. The methods for obtaining the absorption
spectra data haec been described already from this
Laboratory." For'the sake of simplicity not all
the experimental points are shown in the curves.
JOURNAL, 4#, 853 (1927).
(11) Acly and Freach, THIS
(CONTRIBUTION FROM THE CHEMICAL LABORATORIES
OF HARVARD
The Solubility of Barium Nitrate in Concentrated Nitric Acid
BY CHARLES
H. GREENE
The determinations of the solubility of barium
nitrate in nitric acid described in this paper were
undertaken because Df the value of this system for
analytical purposes. The use of concentrated
nitric acid to separate barium and strontium from
calcium was first suggested by Rawson.' It is
very convenient for the qualitative analysis of the
alkaline earth group.2 Willard and Goodspeed3
have recently introduced a new technique for the
precipitation of lead, barium, and strontium with
100% nitric acid and have shown that these metals
may be separated quantitatively from calcium and
most other metals by means of this reagent.
A number of ix~v&+tigators~-~ have measured the
solubility of barium' 'nitrate in dilute nitric acid
but no quantitative data appear to be available
for concentrations of nitric acid above 5070, the
range which is of interest for analytical purposes.
Experimental
Barium nitrate of reagent grade was purified by four
recrystallizations with rinsing and centrifugal drainage.
- was 0.003% while most of the samples contained less than
(1) Rowson, 1. SOC.Chcm. I n d . , 16, 113 (1897).
(a) Greene, I n d . En& Chcm,, Anal. Ed.,I, 348 (1938).
(3) Willard and Goodspeed, ibid., 8 , 414 (1938).
(4) Chlopin, Z.anorg. altgcm. Chcm., ill, 108 (1925).
(5) Fricke and Brummcr, ibid , 11%319 (1933).
(8) Friend and Wheat, J . Ckcm SOC, 601-2 (1933).
(7) Masson, ibid., be, 1122 (1911)
(8) Tolrnachev, Compl rend acad sci. U . R S . S , 689 (1930A)
VOl. 59
Table I summarizes the values of log e at intervals
of 100 A. wave lengths, as well as the positions of
the significant absorption maxima.
Summary
1. Absorption spectra curves are shown for the
effect of solvent on nitrosobenzene, l-nitrosonaph-
thalene, 1,2-naphthoquinone dioxime, and the
three nitrosonaphthols.
2. From solvent effects, and from comparison
of curves of compounds of fixed quinonoid and of
fixed benzenoid structure, evidence is given for the
state of the quinonoid-benzenoid equilibrium in
the three nitrosonaphthols.
3. No very definite conclusions are possible
without further work, but the quinonoid modifi-
cation seems to predominate in the equilibria
studied.
WELLESLEY,MASS. RECEIVED
JANUARY 14, 1937
UNIVERSITY AND RADCLIFFE COLLEGE]
C. P. nitric acid, either fuming or concentrated as required,
was purified by two or more distillations in an all glass
still evacuated by a glass aspirator. Conductivity water,
analytical reagent sodium carbonate and c. P. sulfuric
acid were used.
Preliminary results upon the solubility of strontium
nitrate in concentrated nitric acid indicated a slightly
greater solubility in acid which had been exposed to full
daylight for sixteen hours with consequent decomposition.
For this reason, the acid for these experiments was dis-
tilled in a dark room and exposed only to red light. The
solubility flasks were protected from white light a t all
times. All of the solutions containing more than 50%
nitric acid were analyzed for nitrous acid by the following
method.
Samples of 25.00 ml. taken from the flasks after the
filtration of the saturated solution, were diluted with 100
ml. of water and oxidized for twenty minutes with 10.00
ml. of 0.1 N potassium permanganate. The excess per-
manganate was reduced with 10.00 ml. of 0.1 N oxalic
acid and the oxalic acid back titrated with 0.1 N per-
manganate. The oxalic acid and permanganate solutions
were compared each time by blank runs with 25 ml. of
18 N sulfuric acid in place of the nitric acid solution.
The largest amount of nitrous acid found in any sample
0.001%. I t was thought that this small amount of de-
composition would be without appreciable influence on
the solubilities measured.
Sealed Pyrex Erlenmeyer flasks containing the acid
with a liberal excess of solid barium nitrate were rotated
about an inclined axis for twenty-four hours or more in a
July, 1937 SOLUBILITY
OF BARIUM
NITRATE
IN CONCENTRATED
NITRICACID 1187

thermostat at 24.88 =t0.02'. Preliminary experiments a quartz capsule. The crucible was weighed against a
indicated that equilibrium was reached in four hours. tare of similar material upon a micro balance reliable to
The thermometer was compared with one calibrated by a few thousandths of a milligram.
the Bureau of Standards. The ilasks were then allowed The precipitates were examined-with a quartz spectro-
to settle for a t least twelve hours in the thermostat. In graph and found to be free from significant quantities of
the experiments a t 0" the Basks were shaken and allowed metals other than barium. WFights and volumetric
to settle with ice and water in large Dewar jars for the apparatus were standardized. W?ights have been reduced
same lengths of time. to vacuum.
Without removing the flasks from the thermostat they
were opened by applying a hot glass rod to a scratch on Results
the neck. Samples were withdrawn through sintered The results of these determinations are given in
Pyrex filters directly into calibrated 250-ml.volumetric
flasks.
Table I and are plotted in Fig. 1 upon a logarith-
Small samples withdrawn in adjusting the solutions mic scale. The results of Tolmyhev,8which have
to the mark in the 250-ml. flasks served for the deter- also been plotted in Fig. 1, are consistent with the
ruination of nitric acid. After weighing, these were diluted results of the present investigation for the concen-
with great care to avoid loss by evaporation. They were tration range which they cover. The results a t 0 '
titrated with 0.5 N carbonate free sodium hydroxide
indicate that the temperature coefficient of solu-
measured in weight burets. The sodium hydroxide was
stored in a paraffin lined bottle and standardized fre- bility is moderate in this system so that little is to
quently against constant boiling hydrochloric acid. The be gained from an analytical point of view by
average difference between duplicate analyses for nitric cooling.
acid was 0.03%.
Densities were determined by weighing the 250-ml. TABLE
I
flasks filled with the solutions. Unfortunately the tem- THE SoLUBILITY OF BARIUMNITRATEIN NITRIC ACID
peratures of the filtrates changed somewhat during the Temperature, 24.88"
slow filtrations so that the densities are less accurate "08,
%
Density,
g./ml.
Ba(NOd9,
mg./l.
Ba(NOa)e, 6
%
+ log (%Ba(NCh)n)
Exptl. Calcd.
than would otherwise have been the case. The room
temperature, however, was close to 25" during the filtra- 0.00 1.0769 99,400' 9 23 6.97" . .
tions so that the errors in the densities reported are in 20.65 1.1221 5,560' 0.495 5.69" . .
ihe last decimal place. The solutions saturated a t 0" were 32.71 1.1966 2,380' ,199 5.30" . .
brought to 24.88' before adjusting the volume to 250 ml. 47.60 1.2907 624b ,0484 4.68" . .
The weighed samples of the concentrated nitric acid 56.60 1.343 197 .014$ 4.17 4.18
solutions were transferred quantitatively from the volu- 56.98 1.346 187 0139 4.14 4.15
metric flasks to one liter distilling flasks with long necks 59.06 1.355 136 ,0100 4.00 3.99
constricted to fit directly to Pyrex condenser tubes. 61.67 1.372 8i.3 .00836 3.80 3.79
Ninety per cent. of the acid was removed and recovered 62.77 1.373 72.8 .00532 3.73 3.70
by distillation. Experiments in which the first distillate 64.36 1.385 51.5 .00372 3.57 3.57
was redistilled proved that there was no loss of barium
nitrate when the solutions were distilled in this apparatus.
66.05 1.394 33.5 .W 4 1 3.38 3.43
67.12 1.394 31.7 .00228 3.36 3.34
The remaining 10% of the acid solution was rinsed
67.30 1.395 31.0 .w23 3.35 3.33
quantitatively into a small beaker and evaporated to
71.15 1.413 14.1 .00100 3.00 2.99
dryness in a stream of filtered air. The residue of barium
71.45 1.415 12.2 .GO0865 2..94 2.96
nitrate was dissolved in water with the addition of a drop
of nitric acid. The solution was filtered through a tiny 75.14 1.430 5.78 ,000404 2.61 2.61
filter arranged so that the filtrate ran directly into hot 78.29 1.445 2.87 .o00199 2.30 2.30
dilute sulfuric acid in a small platinum crucible. 78.51 1.442 2.85 .000197 2.29 2.28
Any insoluble residue in the beaker was scrubbed out 85.37 1.463 0.376 .oooO257 1.41' 1.56
with bits of quantitative iilter paper and ashed with the 91.69 1.485 ,108 ,0000072 0.86" 0.85
filter. Barium in this residue was converted to barium 92.10 1.480 .283 . oooo191 1.28" .80
carbonate by fusion with a small amount of sodium car-
Temperature, 0.00"
bonate. The melt was dissolved in water and any barium
carbonate present filtered off on another tiny filter and 56.42 1.3416 132 0.00982 3.99 3.99
washed a few times with small portions of water to remove 59.00 1.3558 86.1 .0(?635 3.80 3.80
most of the sodium carbonate solution. It was then 63.21 1.3763 30.8 .00224 3.35" 3.47
dissolved with a few drops of dilute nitric acid and washed 67.88 1.3975 16.5 .00118 3.07 3.07
into the crucible in which the main part of the barium 71.93 1.4143 7.15 .000506 2.70 2.70
had already been precipitated as sulfate. 72.82 1.4177 5.75 .o00406 2.61 2.61
After the precipitate had been digested sufficiently These experiments were omitted in computing the
the supernatant liquid was drawn off through a fine coefficients for equations (1) and (2).
porcelain filter stick. The precipitate was washed with These values were obtained by evaporating 58-ml.
0.06 N sulfuric acid and dried by heating the crucible in samples to dryness and weighing the residue.
1188 ROGER6. BATESAND WARRENC. VOSBURG~ VOl. 59

function were determined by the method of least

squares omitting the points above 80% of acid
l . 0 P because of the obvious experimental uncertainties
in this range. The resulting equations have been
used to compute the values in column 6 of Table
I and the solubilities at round concentrations of
nitric acid in Table 11.
# I 0.0001 -
At 24.88’ the solubility is given by the equatioii
log( % Ba(NO&) = 0.24537 -0.0006232 (% “03)
-0.0006351 ( % HNOJa ( I )
while a t 0.00’ the equation is
0 20 40 60 80 100
70 “08. log( % Ba(N0a)Z) = -0.53778 +
0.0189055(% “ 0 8 )
Fig. 1.-The solubility of barium nitrate in flitric -0.00079706 (% “08)’ (2)
acid: 0, experiments a t 24.88’; 0 , experiments a t These equations represent well the results of the
0.00’; +,
experiments of Tolmachev.8
present experiments in the concentration range
From 55 to 80% of nitric acid the logsrithms of from 50 to 90% nitric acid. As is shown by the
the solubilities fall upon a smooth curve which dashed curve in Fig. 1 they are entirely unreliable
may be expressed well by a quadratic function of in dilute nitric acid. The extrapolation to 100%
the per cent. of nitric acid. Coefficients for this HNOI in Table I1 is interesting but uncertain.
TABLEI1
THE SOLUBILITY OF BARIUMNITRATE IN NITRICACID
Summary
CALCULATED BY EQUATIONS(1) AND (2) The solubility of barium nitrate has been meas-
” 0 2 , %24.88OC.
Ba(N0a)z %0.OO~C.
Ba(NO8)z ured at 0.00 and 24.88’ in concentrations of ni-
%
50 0.0423 0.0260 tric acid ranging up to 92%. Equations have
60
70
.00&35
LO0 123
00533
000769
-
been derived which express the logarithm of the
solubility as a quadratic function of the per cent.
80 ,000135 ,0000747
90 .0000111 ( .00000509)
of acid.
100 ( .00000068) i .oooooo24j CAMBRIDGE,
MASS. APRIL22, 1937
RECEIVED

[CONTRIBUTION FROM THE DEPARTMENT

OF CHEMISTRY OF DUKEUNIVERSITY]

The Normal Potential of the Mercury-Mercurous Iodide Electrode at 29”

BY ROGERG. BATESAND WARRENC. VOSBURGH

For the normal potential of the mercury-mer-
curous iodide electrode, the value of 0.0416 V. a t
2 5 O is given by “International Critical Tables.”2
This value was calculated from the electromotive
force of the lead-mercurous iodide cell measured
by Vosburgh3 and a value for the normal poten-
tial of the lead amalgam-lead iodide electrode.
However, values for the latter electrode calculated
from data for different cells4do not agree well. In
(1) P a r t Of a thesis Bubmitted by Roger G. Bates in partial ful-
filment of the requiremeats for the degree of Doctor of PhilbsQphy
in t h e Graduate School of Arts and Sciences of Duke University
(2) “fntertlational Critical Tables,” Vol VI, p 332
(3) Voshurgh, THIS J O U ~ N A L ,10, 2391 (1928).
(4) (a) Oerke, i b i d , 44, 1701-1703 (1922). (b) Getman, J Phbc
C hem , S a , 944 (1928), (c) Jones and Kaplan. THISJOURNAI ,10, 2076
(1928). (d) Owen, r b r d , 67, 1526 (1935)
view of the resulting uncertainty, it was decided
to determine the normal potential of the mercu-
rous iodide electrode directly, since its value was
needed in another investigation.
Materials.-Mercury was purified by washing with an
acidified mercurous nitrate solution and distilling twice
a t reduced pressure in a current of air. Mercurous iodide
was prepared by precipitation and digestion as described
by Vosburgha for his Preparation 7. Potassium iodide
was recrystallized twice from redistilled water and dried
for about a week at 110-125”. Analysis by the Volhard
method indicated a purity of a t least 99.9%. Hydrogen
was prepared by the electrolysis of 3070 sodium hydroxide
solution and was passed through a tube containing a hot
platinum wire for removal of oxygen.
Preparation and Measurement of the Cells.-Two series
of cells were made, one with electrolytes of potassium